Poly(ethylene oxide) (PEO) is a promising solid-state polymer electrolyte (SPE), but its room-temperature crystallization leads to low ionic conductivity, limiting its application. Semi-interpenetrating networks (semi-IPNs) represent an effective strategy for suppressing PEO crystallization. Previous studies have overlooked the influence of crosslinking temperature on the network topology. Here, we report a crosslinking temperature-regulated topological confinement of amorphous PEO electrolyte achieved by initiating the photopolymerization of ethoxylated trimethylolpropane triacrylate (ETPTA) at 80 °C. The resulting homogeneous network effectively confines the amorphous phase of PEO while retaining local freedom for Na+ transport. When the mass ratio of PEO to ETPTA is 60:40 (P-E40H), the material exhibits optimal comprehensive electrochemical performance, demonstrating a high room-temperature ionic conductivity of 0.173 mS cm–1, a high Na+ transference number of 0.59, high voltage stability of 4.72 V, and an elongation at break of 160.05%. Molecular dynamics simulations indicate that the uniform network allows Na+ to adopt a solvation structure dominated purely by PEO. The capacity retention ratios of Na3V2(PO4)3|P-E40H|Na cell are 92.9% (1 C, 400 cycles) and exhibits a specific capacity of 64.05 mAh g–1 at 5 C. This work demonstrates that crosslinking temperature is an effective processing parameter for tuning the network topology of semi-IPN electrolytes, offering a simple and efficient structural regulation strategy for high-performance solid-state sodium-metal batteries.
聚环氧乙烷（PEO）是一种很有前途的固态聚合物电解质（SPE），但其室温结晶导致离子电导率低，限制了其应用。半互穿网络（semi-IPNs）是抑制PEO结晶的有效策略。以往的研究忽略了交联温度对网络拓扑结构的影响。在这里，我们报道了一种交联温度调节的无定形PEO电解质的拓扑限制，通过在80°C下引发乙氧基化三甲基丙烷三丙烯酸酯（ETPTA）的光聚合。由此产生的均匀网络有效地限制了PEO的非晶相，同时保留了Na+输运的局部自由。当PEO与ETPTA的质量比为60:40 （P-E40H）时，该材料的综合电化学性能最佳，室温离子电导率为0.173 mS cm-1， Na+转移数为0.59，电压稳定性为4.72 V，断裂伸长率为160.05%。分子动力学模拟表明，均匀的网络使得Na+采用纯PEO主导的溶剂化结构。Na3V2(PO4)3|P-E40H|钠电池的容量保持率为92.9%（1℃，400次循环），在5℃时的比容量为64.05 mAh g-1。本研究表明，交联温度是调节半ipn电解质网络拓扑结构的有效工艺参数，为高性能固态钠金属电池提供了一种简单有效的结构调节策略。
{"title":"Crosslinking Temperature-Regulated Topological Confinement of Amorphous PEO Electrolytes for High-Performance Sodium-Metal Batteries","authors":"Bolin Li,Hu Fu,Yuping Wu,Zhirong Chen,Haichen Li,Qinran Zhang,Hongming Zhou","doi":"10.1021/acsami.6c21141","DOIUrl":"https://doi.org/10.1021/acsami.6c21141","url":null,"abstract":"Poly(ethylene oxide) (PEO) is a promising solid-state polymer electrolyte (SPE), but its room-temperature crystallization leads to low ionic conductivity, limiting its application. Semi-interpenetrating networks (semi-IPNs) represent an effective strategy for suppressing PEO crystallization. Previous studies have overlooked the influence of crosslinking temperature on the network topology. Here, we report a crosslinking temperature-regulated topological confinement of amorphous PEO electrolyte achieved by initiating the photopolymerization of ethoxylated trimethylolpropane triacrylate (ETPTA) at 80 °C. The resulting homogeneous network effectively confines the amorphous phase of PEO while retaining local freedom for Na+ transport. When the mass ratio of PEO to ETPTA is 60:40 (P-E40H), the material exhibits optimal comprehensive electrochemical performance, demonstrating a high room-temperature ionic conductivity of 0.173 mS cm–1, a high Na+ transference number of 0.59, high voltage stability of 4.72 V, and an elongation at break of 160.05%. Molecular dynamics simulations indicate that the uniform network allows Na+ to adopt a solvation structure dominated purely by PEO. The capacity retention ratios of Na3V2(PO4)3|P-E40H|Na cell are 92.9% (1 C, 400 cycles) and exhibits a specific capacity of 64.05 mAh g–1 at 5 C. This work demonstrates that crosslinking temperature is an effective processing parameter for tuning the network topology of semi-IPN electrolytes, offering a simple and efficient structural regulation strategy for high-performance solid-state sodium-metal batteries.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"82 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149250811","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Controlling the in-plane orientation of two-dimensional nanosheets during repeated forming remains challenging because deformation can become nonuniform through the film thickness. Here, alternating 60 and 80 wt % boron nitride nanosheet/thermoplastic polyurethane (BNNS/TPU) layers were used to introduce a moderate modulus contrast during water-based stack pressing and were compared with homogeneous 70 wt % films having the same nominal average filler content. Repeated pressing increased BNNS alignment in both architectures, while the binary film exhibited a slightly narrower SEM-derived angular distribution after six total pressing operations. The binary film reached an in-plane thermal conductivity of 17.85 W m–1·K–1, a through-plane thermal conductivity of 0.22 W m–1 K–1, a tensile strength of 17.48 MPa, and a thermal anisotropy ratio of approximately 81. Under the present point-heating configuration, its hotspot temperature was 5.7 °C lower than that of the unitary film at 60 s. Idealized linear-elastic finite-element analysis qualitatively illustrates modulus-dependent stress and strain partitioning but does not model interfacial damage or nanosheet rotation. Fabrication of 400 × 400 mm films further demonstrates large-area batch-processing feasibility.
在重复成形过程中，控制二维纳米片的面内取向仍然是一个挑战，因为变形会随着薄膜厚度的变化而变得不均匀。在这里，60和80 wt %氮化硼纳米片/热塑性聚氨酯（BNNS/TPU）层交替使用，以在水基堆压过程中引入适度的模量对比，并与具有相同标称平均填料含量的70 wt %均匀薄膜进行比较。在这两种结构中，重复的压制增加了BNNS的取向，而在总共六次压制操作后，二元薄膜的sem衍生角分布略窄。二元膜的面内导热系数为17.85 W m-1·K-1，通面导热系数为0.22 W m-1 K-1，抗拉强度为17.48 MPa，热各向异性比约为81。在当前点加热结构下，其热点温度在60 s时比单一膜低5.7℃。理想的线弹性有限元分析定性地说明了模量依赖的应力和应变分配，但不模拟界面损伤或纳米片旋转。400 × 400毫米薄膜的制备进一步证明了大面积批量加工的可行性。
{"title":"Green Manufacturing of High-Performance Multilayered Boron Nitride Composites via Modulus-Contrast-Assisted Stack Pressing","authors":"Peiyao Ran,Youxing Shu,Fangzheng Zhen,Siyuan Ding,Yu Du,Yueni Zhong,Qixuan Deng,Miheng Dong,Song Huang,Zhijun Guo,Weiren Fan,Ruiping Zou,Aibing Yu,Ling Qiu,Minsu Liu","doi":"10.1021/acsami.6c17025","DOIUrl":"https://doi.org/10.1021/acsami.6c17025","url":null,"abstract":"Controlling the in-plane orientation of two-dimensional nanosheets during repeated forming remains challenging because deformation can become nonuniform through the film thickness. Here, alternating 60 and 80 wt % boron nitride nanosheet/thermoplastic polyurethane (BNNS/TPU) layers were used to introduce a moderate modulus contrast during water-based stack pressing and were compared with homogeneous 70 wt % films having the same nominal average filler content. Repeated pressing increased BNNS alignment in both architectures, while the binary film exhibited a slightly narrower SEM-derived angular distribution after six total pressing operations. The binary film reached an in-plane thermal conductivity of 17.85 W m–1·K–1, a through-plane thermal conductivity of 0.22 W m–1 K–1, a tensile strength of 17.48 MPa, and a thermal anisotropy ratio of approximately 81. Under the present point-heating configuration, its hotspot temperature was 5.7 °C lower than that of the unitary film at 60 s. Idealized linear-elastic finite-element analysis qualitatively illustrates modulus-dependent stress and strain partitioning but does not model interfacial damage or nanosheet rotation. Fabrication of 400 × 400 mm films further demonstrates large-area batch-processing feasibility.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"166 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149248541","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yantao Deng,Songkun Zeng,Yufeng Xie,Wenbin Huang,Zikai He
Achieving deep-blue electroluminescence with high efficiency and color purity that meets the BT.2020 standard remains a major challenge for organic light-emitting diodes. Here, we report two D–π–A emitters, SFIA-1 and SFIA-2, based on a spiro-fluorene-imidazole acceptor (A) and a 10H-spiro(acridine-9,9′-fluorene) donor (D). By strategically introducing a para-phenylene bridge, the molecules adopt highly twisted conformations. Experimental and theoretical analyses further reveal CT-dominated, hybridized local-excited and charge-transfer states. Both emitters exhibit wide optical band gaps (>3.3 eV). A negligible singlet–triplet energy gap of 0.01 eV, combined with a moderate spin–orbit coupling, activates an efficient high-lying reverse intersystem crossing “hot exciton” channel. As a result, the SFIA-1-doped device achieves a maximum external quantum efficiency (EQE) of 7.53% with an electroluminescence peak at 425 nm, while SFIA-2 delivers an electroluminescence peak at 420 nm with Commission Internationale de l'Éclairage coordinates of (0.159, 0.043), closely aligned with the BT.2020 blue light standard. Furthermore, the non-doped devices based on SFIA-1 and SFIA-2 exhibit maximum EQEs of 6.29 and 10.89%, respectively. Therefore, SFIA-2 was utilized as a host for PO-01-TB, tCzphB-Ph, and Ir(mphmq)2(tmd) emitters, yielding maximum EQEs of 30.47, 24.09, and 15.57%, respectively. These results demonstrate a molecular design strategy for ultra-deep-blue hot-exciton materials and high-performance hosts that reconciles the trade-off between exciton utilization efficiency and color purity.
实现符合BT.2020标准的高效率和色纯度的深蓝色电致发光仍然是有机发光二极管的主要挑战。在这里，我们报道了两个D -π-A发射体，SFIA-1和SFIA-2，基于一个螺-芴-咪唑受体(a)和一个10h -螺（吖啶-9,9 ' -芴）供体(D)。通过巧妙地引入对苯基桥，分子采用高度扭曲的构象。实验和理论分析进一步揭示了ct主导、杂化的局部激发态和电荷转移态。两个发射体都表现出较宽的光学带隙（>3.3 eV）。一个可以忽略不计的0.01 eV的单重态-三重态能隙，加上适度的自旋-轨道耦合，激活了一个高效的高空反向系统间穿越“热激子”通道。结果表明，sfia -1掺杂器件的最大外量子效率（EQE）为7.53%，电致发光峰值为425 nm，而SFIA-2的电致发光峰值为420 nm，国际委员会（Commission Internationale del 'Éclairage）坐标为（0.159,0.043），与BT.2020蓝光标准密切相关。此外，基于SFIA-1和SFIA-2的未掺杂器件的最大EQEs分别为6.29%和10.89%。因此，利用SFIA-2作为PO-01-TB、tCzphB-Ph和Ir(mphmq)2（tmd）发射体的宿主，获得的最大EQEs分别为30.47%、24.09和15.57%。这些结果证明了一种超深蓝色热激子材料和高性能宿主的分子设计策略，该策略可以协调激子利用效率和颜色纯度之间的权衡。
{"title":"Deep-Blue Hot Exciton Emitters Approaching the BT.2020 Standard: Spiro-Fluoreno-Imidazole Acceptors with Twisted D–π–A Architectures","authors":"Yantao Deng,Songkun Zeng,Yufeng Xie,Wenbin Huang,Zikai He","doi":"10.1021/acsami.6c16895","DOIUrl":"https://doi.org/10.1021/acsami.6c16895","url":null,"abstract":"Achieving deep-blue electroluminescence with high efficiency and color purity that meets the BT.2020 standard remains a major challenge for organic light-emitting diodes. Here, we report two D–π–A emitters, SFIA-1 and SFIA-2, based on a spiro-fluorene-imidazole acceptor (A) and a 10H-spiro(acridine-9,9′-fluorene) donor (D). By strategically introducing a para-phenylene bridge, the molecules adopt highly twisted conformations. Experimental and theoretical analyses further reveal CT-dominated, hybridized local-excited and charge-transfer states. Both emitters exhibit wide optical band gaps (>3.3 eV). A negligible singlet–triplet energy gap of 0.01 eV, combined with a moderate spin–orbit coupling, activates an efficient high-lying reverse intersystem crossing “hot exciton” channel. As a result, the SFIA-1-doped device achieves a maximum external quantum efficiency (EQE) of 7.53% with an electroluminescence peak at 425 nm, while SFIA-2 delivers an electroluminescence peak at 420 nm with Commission Internationale de l'Éclairage coordinates of (0.159, 0.043), closely aligned with the BT.2020 blue light standard. Furthermore, the non-doped devices based on SFIA-1 and SFIA-2 exhibit maximum EQEs of 6.29 and 10.89%, respectively. Therefore, SFIA-2 was utilized as a host for PO-01-TB, tCzphB-Ph, and Ir(mphmq)2(tmd) emitters, yielding maximum EQEs of 30.47, 24.09, and 15.57%, respectively. These results demonstrate a molecular design strategy for ultra-deep-blue hot-exciton materials and high-performance hosts that reconciles the trade-off between exciton utilization efficiency and color purity.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"1 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149250809","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tianhao Xu,Xuemeng Fu,Liquan Wang,Liangshun Zhang,Jiaping Lin
Optimizing the properties of thermosetting polymers presents an inherent challenge due to the high-dimensional formulation-processing parameter space and the trade-offs between thermomechanical properties. In this contribution, we propose a hierarchical Monte Carlo tree search (MCTS)-guided Bayesian optimization (BO) framework to enable the simultaneous design of both the composition and curing protocols of epoxy resins as a major class of thermosetting polymers. A sigmoid-based weighting strategy is introduced to encode application-driven performance thresholds into the objective function, guiding the optimization toward coordinated multi-property improvement. With only 30 experiments across four iterative rounds, the framework optimizes both the formulation and curing protocols to yield a performance-enhanced epoxy resin that simultaneously meets all four target thresholds. This balanced performance cannot be achieved by any of the initial samples, an equal-weight baseline, or commercial and literature-reported systems. Furthermore, interpretable machine learning analysis combined with targeted experimental validation quantitatively resolves the relative importance of formulation and processing parameters, indicating that composition variables dominate overall property trends while their synergistic interactions produce non-linear effects on glass transition temperature. The findings demonstrate that the hierarchical MCTS-guided BO framework offers an efficient strategy for navigating complex formulation-processing spaces, and the interpretable analysis provides a quantitative basis for understanding structure–property relationships in thermosetting polymers.
{"title":"Hierarchical MCTS-Guided Bayesian Optimization for Co-designing Formulation and Processing of Thermosetting Polymers with Balanced Performance","authors":"Tianhao Xu,Xuemeng Fu,Liquan Wang,Liangshun Zhang,Jiaping Lin","doi":"10.1021/acsami.6c18158","DOIUrl":"https://doi.org/10.1021/acsami.6c18158","url":null,"abstract":"Optimizing the properties of thermosetting polymers presents an inherent challenge due to the high-dimensional formulation-processing parameter space and the trade-offs between thermomechanical properties. In this contribution, we propose a hierarchical Monte Carlo tree search (MCTS)-guided Bayesian optimization (BO) framework to enable the simultaneous design of both the composition and curing protocols of epoxy resins as a major class of thermosetting polymers. A sigmoid-based weighting strategy is introduced to encode application-driven performance thresholds into the objective function, guiding the optimization toward coordinated multi-property improvement. With only 30 experiments across four iterative rounds, the framework optimizes both the formulation and curing protocols to yield a performance-enhanced epoxy resin that simultaneously meets all four target thresholds. This balanced performance cannot be achieved by any of the initial samples, an equal-weight baseline, or commercial and literature-reported systems. Furthermore, interpretable machine learning analysis combined with targeted experimental validation quantitatively resolves the relative importance of formulation and processing parameters, indicating that composition variables dominate overall property trends while their synergistic interactions produce non-linear effects on glass transition temperature. The findings demonstrate that the hierarchical MCTS-guided BO framework offers an efficient strategy for navigating complex formulation-processing spaces, and the interpretable analysis provides a quantitative basis for understanding structure–property relationships in thermosetting polymers.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"10 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149250810","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jingkun Gu,Haojie Han,Zihao Zheng,Tianyi Liu,Zongqi Xu,Jinming Guo,Jing Ma
SrTiO3 (STO), a typical quantum paraelectric material, has been extensively investigated for the stabilization of ferroelectric order through external perturbations. However, conventional approaches typically rely on epitaxial strain or external field excitation, limiting their suitability for epitaxial-strain-free and low-stress device architectures. Here, we demonstrate an epitaxial-strain-independent route to robust ferroelectricity in STO enabled by interfacial oxygen-vacancy engineering. By introducing a La0.5Sr0.5MnO3 (LSMO) bottom electrode with strong oxygen affinity, interfacial oxygen redistribution is promoted during epitaxial growth, resulting in significant oxygen-vacancy accumulation in the adjacent STO layer. The engineered oxygen vacancies drive local symmetry breaking and stabilize polar nanoregions in fully relaxed STO epitaxial films. Consequently, STO grown on the LSMO buffer layer exhibits robust room-temperature ferroelectricity with a remanent polarization of 14 μC/cm2, achieved without conventional epitaxial strain engineering. These findings establish interfacial oxygen-vacancy engineering as a viable strategy for inducing ferroelectricity in STO-based heterostructures and provide a possible route for designing emergent functionalities.
{"title":"Oxygen-Vacancy-Engineered Robust Ferroelectricity in Epitaxial-Strain-Free SrTiO3 Films","authors":"Jingkun Gu,Haojie Han,Zihao Zheng,Tianyi Liu,Zongqi Xu,Jinming Guo,Jing Ma","doi":"10.1021/acsami.6c12589","DOIUrl":"https://doi.org/10.1021/acsami.6c12589","url":null,"abstract":"SrTiO3 (STO), a typical quantum paraelectric material, has been extensively investigated for the stabilization of ferroelectric order through external perturbations. However, conventional approaches typically rely on epitaxial strain or external field excitation, limiting their suitability for epitaxial-strain-free and low-stress device architectures. Here, we demonstrate an epitaxial-strain-independent route to robust ferroelectricity in STO enabled by interfacial oxygen-vacancy engineering. By introducing a La0.5Sr0.5MnO3 (LSMO) bottom electrode with strong oxygen affinity, interfacial oxygen redistribution is promoted during epitaxial growth, resulting in significant oxygen-vacancy accumulation in the adjacent STO layer. The engineered oxygen vacancies drive local symmetry breaking and stabilize polar nanoregions in fully relaxed STO epitaxial films. Consequently, STO grown on the LSMO buffer layer exhibits robust room-temperature ferroelectricity with a remanent polarization of 14 μC/cm2, achieved without conventional epitaxial strain engineering. These findings establish interfacial oxygen-vacancy engineering as a viable strategy for inducing ferroelectricity in STO-based heterostructures and provide a possible route for designing emergent functionalities.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"13 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149248548","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Metal-organic terephthalates composed of earth-abundant elements are promising low-cost and structurally tuneable anodes for sodium-ion batteries, yet their electrochemical behavior, particularly in newly developed compounds, remains insufficiently understood. We report monoclinic nanocrystalline ZnC8H4O4 (ZnTP-2), prepared through the controlled thermal transformation of a hydrated zinc terephthalate precursor, ZnC8H6O5 (ZnTP-1), containing residual terephthalic acid (ZnTP-1@TPA). This transformation involves TPA sublimation and framework dehydration, producing ZnTP-2 with fine crystals of approximately 50–150 nm, increased surface area, and a higher concentration of oxygen-related defect sites compared with ZnTP-1@TPA. ZnTP-2 delivers a reversible Na-ion storage capacity of 222.7 mAh g–1 after 80 cycles at 50 mA g–1, approaching its theoretical capacity and indicating highly efficient utilization of the terephthalate redox framework. It also retains 110 mAh g–1 after 500 cycles at 1000 mA g–1, with a relatively low charge-transfer resistance of 11.5 Ω, demonstrating improved electrochemical stability and rate performance compared with conventional metal-organic terephthalate anodes. Electrochemical kinetic analyses reveal Na-ion diffusion coefficients between 10–14 and 10–12 cm2 s–1, with the differences discussed in terms of apparent, Warburg-related and bulk/chemical diffusion processes. UV–vis analysis reveals a lower optical band gap for ZnTP-2 (2.74 eV) than for ZnTP-1@TPA (3.36 eV), with DFT calculations on idealized molecular models of hydrated and dehydrated zinc terephthalates supporting a similar trend. Full-cell examination provides proof of concept for its applicability.
金属-有机对苯二甲酸盐是一种很有前途的低成本、结构可调的钠离子电池阳极，但其电化学行为，特别是在新开发的化合物中，仍未得到充分的了解。我们报道了单斜纳米晶ZnC8H4O4 (ZnTP-2)，通过水合对苯二甲酸锌前驱体ZnC8H6O5 （ZnTP-1）的受控热转化制备，含有残留的对苯二甲酸（ZnTP-1@TPA）。这种转变包括TPA升华和框架脱水，产生的ZnTP-2具有约50-150 nm的细晶，比ZnTP-1@TPA表面积增加，氧相关缺陷位点浓度更高。ZnTP-2在50 mA g-1下循环80次后可提供222.7 mAh g-1的可逆钠离子存储容量，接近其理论容量，表明对苯二甲酸盐氧化还原框架的高效利用。在1000 mA g-1下循环500次后，它还能保持110 mAh g-1，电荷转移电阻相对较低，为11.5 Ω，与传统的金属有机对苯二甲酸盐阳极相比，显示出更好的电化学稳定性和速率性能。电化学动力学分析表明，na离子扩散系数在10-14和10-12 cm2 s-1之间，并从表观扩散、warburg相关扩散和体/化学扩散过程中讨论了差异。UV-vis分析显示ZnTP-2的光学带隙（2.74 eV）比ZnTP-1@TPA （3.36 eV）低，水合和脱水对苯二甲酸锌的理想分子模型的DFT计算也支持类似的趋势。全细胞检查为其适用性提供了概念证明。
{"title":"Thermally Transformed ZnC8H4O4 Nanocrystals for Enhanced Sodium-Ion Storage","authors":"Yunan Liu,Ali Reza Kamali","doi":"10.1021/acsami.6c16944","DOIUrl":"https://doi.org/10.1021/acsami.6c16944","url":null,"abstract":"Metal-organic terephthalates composed of earth-abundant elements are promising low-cost and structurally tuneable anodes for sodium-ion batteries, yet their electrochemical behavior, particularly in newly developed compounds, remains insufficiently understood. We report monoclinic nanocrystalline ZnC8H4O4 (ZnTP-2), prepared through the controlled thermal transformation of a hydrated zinc terephthalate precursor, ZnC8H6O5 (ZnTP-1), containing residual terephthalic acid (ZnTP-1@TPA). This transformation involves TPA sublimation and framework dehydration, producing ZnTP-2 with fine crystals of approximately 50–150 nm, increased surface area, and a higher concentration of oxygen-related defect sites compared with ZnTP-1@TPA. ZnTP-2 delivers a reversible Na-ion storage capacity of 222.7 mAh g–1 after 80 cycles at 50 mA g–1, approaching its theoretical capacity and indicating highly efficient utilization of the terephthalate redox framework. It also retains 110 mAh g–1 after 500 cycles at 1000 mA g–1, with a relatively low charge-transfer resistance of 11.5 Ω, demonstrating improved electrochemical stability and rate performance compared with conventional metal-organic terephthalate anodes. Electrochemical kinetic analyses reveal Na-ion diffusion coefficients between 10–14 and 10–12 cm2 s–1, with the differences discussed in terms of apparent, Warburg-related and bulk/chemical diffusion processes. UV–vis analysis reveals a lower optical band gap for ZnTP-2 (2.74 eV) than for ZnTP-1@TPA (3.36 eV), with DFT calculations on idealized molecular models of hydrated and dehydrated zinc terephthalates supporting a similar trend. Full-cell examination provides proof of concept for its applicability.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"79 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149248542","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Controlling the flow of electricity in metallic circuits with light is a key goal for future optoelectronics. In this work, we demonstrate all-optical generation and directional control of non-thermal drift photocurrents driven by the transfer of spin optical angular momentum to the electron gas of a plasmonic gold wire. We attribute this phenomenon to the Inverse Faraday Effect and show that the current's direction can be precisely reversed at a subwavelength scale by tailoring the incident light's polarization or laser beam position. A bespoke polarization modulation technique is employed to unambiguously separate ultrafast drift currents from the ubiquitous photothermal background. We further reveal a collaborative mechanism where macroscopic thermal gradients, acting as a driving force, are used to extract and remotely detect the locally-generated nanoscale photocurrents. This robust control and detection scheme paves the way for reconfigurable, all-optical nanocircuitry capable of ultrafast on-chip processing.
{"title":"Directional Control of Nonthermal Photocurrents Driven by Optical Spin Angular Momentum","authors":"Roméo Zapata,Diana Singh,Obren Markovic,Chantal Hareau,Xingyu Yang,Ye Mou,Bruno Gallas,Maria Sanz-Paz,Gérard Colas-des-Francs,Alexandre Bouhelier,Mathieu Mivelle","doi":"10.1021/acsami.6c07175","DOIUrl":"https://doi.org/10.1021/acsami.6c07175","url":null,"abstract":"Controlling the flow of electricity in metallic circuits with light is a key goal for future optoelectronics. In this work, we demonstrate all-optical generation and directional control of non-thermal drift photocurrents driven by the transfer of spin optical angular momentum to the electron gas of a plasmonic gold wire. We attribute this phenomenon to the Inverse Faraday Effect and show that the current's direction can be precisely reversed at a subwavelength scale by tailoring the incident light's polarization or laser beam position. A bespoke polarization modulation technique is employed to unambiguously separate ultrafast drift currents from the ubiquitous photothermal background. We further reveal a collaborative mechanism where macroscopic thermal gradients, acting as a driving force, are used to extract and remotely detect the locally-generated nanoscale photocurrents. This robust control and detection scheme paves the way for reconfigurable, all-optical nanocircuitry capable of ultrafast on-chip processing.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"1 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149250917","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Achieving the controllable anomalous valley Hall effect (AVHE) is crucial for valleytronics but remains challenging for bilayer altermagnetic systems. Here, bilayer Mg(FeN)2 is proposed as a stacking-dependent platform for a switchable AVHE. The AA stacking of bilayer Mg(FeN)2 exhibits altermagnetism due to the broken TP(t) symmetry, while the AB stacking is a conventional antiferromagnet protected by TP(t) symmetry. Interestingly, interlayer sliding between AA-1 and AA-2 configurations reverses the out-of-plane ferroelectric polarization and consequently switches the layer-dependent valley polarization. Reversing the magnetic configuration changes the spin occupation of valleys, leading to an opposite Hall voltage signal. Thus, a valleytronic device is constructed for the nonvolatile control of the AVHE. For AB-0 configuration, an external electric field can break layer equivalence and induce layer-dependent valley polarization. Switching the electric field direction or magnetic configuration enables the polarity reversal of the Hall response. This work provides a feasible route for electrically and magnetically controllable AVHE in altermagnets.
{"title":"Switchable Anomalous Valley Hall Effect in Bilayer Mg(FeN)2","authors":"Qiqi Wang,Fei Wang,Li Deng,Chaosheng Hao,Xianmin Zhang","doi":"10.1021/acsami.6c12285","DOIUrl":"https://doi.org/10.1021/acsami.6c12285","url":null,"abstract":"Achieving the controllable anomalous valley Hall effect (AVHE) is crucial for valleytronics but remains challenging for bilayer altermagnetic systems. Here, bilayer Mg(FeN)2 is proposed as a stacking-dependent platform for a switchable AVHE. The AA stacking of bilayer Mg(FeN)2 exhibits altermagnetism due to the broken TP(t) symmetry, while the AB stacking is a conventional antiferromagnet protected by TP(t) symmetry. Interestingly, interlayer sliding between AA-1 and AA-2 configurations reverses the out-of-plane ferroelectric polarization and consequently switches the layer-dependent valley polarization. Reversing the magnetic configuration changes the spin occupation of valleys, leading to an opposite Hall voltage signal. Thus, a valleytronic device is constructed for the nonvolatile control of the AVHE. For AB-0 configuration, an external electric field can break layer equivalence and induce layer-dependent valley polarization. Switching the electric field direction or magnetic configuration enables the polarity reversal of the Hall response. This work provides a feasible route for electrically and magnetically controllable AVHE in altermagnets.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"34 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149248540","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Na Zhou,Yueyue Ma,Yunxia Wang,Fuheng Zhai,Yuanyuan Li,Xiaojun Luo,Bing Shao
Cardiac troponin I (cTnI) serves as a critical biomarker of acute myocardial infarction (AMI). Its serum level is extremely sparse, and the clinical cut-off value reaches merely 0.2 ng mL–1. This poses a significant challenge, requiring highly sensitive analytical techniques for reliable quantification. This study proposes a powerful surface-enhanced Raman scattering (SERS) sensing strategy integrating multistage signal amplification and machine learning to enhance detection performance. By combining T7 RNA polymerase, CRISPR/Cas13a, branched hybridization chain reaction (bHCR), and Fe3O4@COF@Ag magnetic substrate, the strategy constructs an efficient “recognition–amplification–signal output” closed loop for cTnI detection. Experimental results demonstrate that the platform has a linear calibration range of 0.1–104 pg/mL for cTnI, with an estimated limit of detection (LOD) of 0.1 pg/mL, holding promise for future AMI-related biomarker analysis. It also shows excellent selectivity against common serum interferents, good reproducibility (intra-batch RSD = 2.87%, inter-batch RSD = 7.96%), and reliable recovery (100.1%–110%) in human serum samples. Based on Raman signals, the k-nearest neighbor (kNN) classifier demonstrated high accuracy in classifying cTnI concentration levels, while the artificial neural network (ANN) model exhibited strong quantitative predictive performance with an R2 of 0.9997. This platform overcomes the limitations of conventional cTnI assays in terms of sensitivity and signal amplification efficiency, providing a promising analytical platform for future AMI-related biomarker studies.
{"title":"T7 Ribonucleic Acid Polymerase-Triggered CRISPR/Cas13a and Branched HCR Cascade Amplification with Machine Learning for SERS Detection of Cardiac Troponin I","authors":"Na Zhou,Yueyue Ma,Yunxia Wang,Fuheng Zhai,Yuanyuan Li,Xiaojun Luo,Bing Shao","doi":"10.1021/acsami.6c17334","DOIUrl":"https://doi.org/10.1021/acsami.6c17334","url":null,"abstract":"Cardiac troponin I (cTnI) serves as a critical biomarker of acute myocardial infarction (AMI). Its serum level is extremely sparse, and the clinical cut-off value reaches merely 0.2 ng mL–1. This poses a significant challenge, requiring highly sensitive analytical techniques for reliable quantification. This study proposes a powerful surface-enhanced Raman scattering (SERS) sensing strategy integrating multistage signal amplification and machine learning to enhance detection performance. By combining T7 RNA polymerase, CRISPR/Cas13a, branched hybridization chain reaction (bHCR), and Fe3O4@COF@Ag magnetic substrate, the strategy constructs an efficient “recognition–amplification–signal output” closed loop for cTnI detection. Experimental results demonstrate that the platform has a linear calibration range of 0.1–104 pg/mL for cTnI, with an estimated limit of detection (LOD) of 0.1 pg/mL, holding promise for future AMI-related biomarker analysis. It also shows excellent selectivity against common serum interferents, good reproducibility (intra-batch RSD = 2.87%, inter-batch RSD = 7.96%), and reliable recovery (100.1%–110%) in human serum samples. Based on Raman signals, the k-nearest neighbor (kNN) classifier demonstrated high accuracy in classifying cTnI concentration levels, while the artificial neural network (ANN) model exhibited strong quantitative predictive performance with an R2 of 0.9997. This platform overcomes the limitations of conventional cTnI assays in terms of sensitivity and signal amplification efficiency, providing a promising analytical platform for future AMI-related biomarker studies.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"32 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149248543","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ignacio Manuel Argento Arruñada,R. Martín Negri,Michael Kappl
Selective lithium recovery from multication aqueous streams requires translating the high selectivity of lithium-ion-sieve powders into macroscopic materials without compromising the accessibility of their ion-exchange sites. Here, hydrogen manganese oxide (HMO) was localized at the surface of a commercial polyethersulfone (PES) membrane through an adhesive polydopamine (PDA) interlayer, providing direct access to the active phase while preserving the porous membrane architecture. Microscopy and surface analyses confirmed the formation of an HMO-rich interfacial layer, and the resulting PES–PDA–HMO membrane exhibited a Langmuir maximum uptake of 35.6 ± 0.7 mg Li g–1 HMO, corresponding to approximately 91% of the experimentally measured capacity of the free HMO powder (39.1 ± 0.2 mg g–1). Under closed-loop recirculating flow, Li+ uptake approached equilibrium within 6 h and was accompanied by proton release, while X-ray photoelectron spectroscopy directly confirmed Li incorporation into the HMO-containing surface. Lithium removal remained similar across recirculation flow rates of 10–150 mL min–1 under the closed-loop configuration, whereas increasing the HMO surface loading from 5.8 to 8.7 mg cm–2 increased Li+ removal from 68 ± 2 to 99 ± 3% at an initial concentration of 50 ppm. After five adsorption–regeneration cycles using lactic acid at pH 2.1, the membrane retained 90 and 85% of its initial removal performance at 25 and 250 ppm Li+, respectively, with no detectable Mn release. Importantly, selectivity was preserved under severe multication competition: in a solution containing 50 ppm Li+ and 250 ppm each of Co2+, Ni2+, and Mn2+, Li+ removal remained 65 ± 3%, whereas removal of the competing divalent ions remained near 1%. These results demonstrate that interfacial localization of HMO can preserve its ion-exchange functionality after macroscopic immobilization while enabling selective, regenerable lithium capture under dynamic aqueous conditions.
{"title":"Surface-Localized Hydrogen Manganese Oxide Polyethersulfone Membranes for Selective Lithium Capture under Recirculating Flow","authors":"Ignacio Manuel Argento Arruñada,R. Martín Negri,Michael Kappl","doi":"10.1021/acsami.6c16769","DOIUrl":"https://doi.org/10.1021/acsami.6c16769","url":null,"abstract":"Selective lithium recovery from multication aqueous streams requires translating the high selectivity of lithium-ion-sieve powders into macroscopic materials without compromising the accessibility of their ion-exchange sites. Here, hydrogen manganese oxide (HMO) was localized at the surface of a commercial polyethersulfone (PES) membrane through an adhesive polydopamine (PDA) interlayer, providing direct access to the active phase while preserving the porous membrane architecture. Microscopy and surface analyses confirmed the formation of an HMO-rich interfacial layer, and the resulting PES–PDA–HMO membrane exhibited a Langmuir maximum uptake of 35.6 ± 0.7 mg Li g–1 HMO, corresponding to approximately 91% of the experimentally measured capacity of the free HMO powder (39.1 ± 0.2 mg g–1). Under closed-loop recirculating flow, Li+ uptake approached equilibrium within 6 h and was accompanied by proton release, while X-ray photoelectron spectroscopy directly confirmed Li incorporation into the HMO-containing surface. Lithium removal remained similar across recirculation flow rates of 10–150 mL min–1 under the closed-loop configuration, whereas increasing the HMO surface loading from 5.8 to 8.7 mg cm–2 increased Li+ removal from 68 ± 2 to 99 ± 3% at an initial concentration of 50 ppm. After five adsorption–regeneration cycles using lactic acid at pH 2.1, the membrane retained 90 and 85% of its initial removal performance at 25 and 250 ppm Li+, respectively, with no detectable Mn release. Importantly, selectivity was preserved under severe multication competition: in a solution containing 50 ppm Li+ and 250 ppm each of Co2+, Ni2+, and Mn2+, Li+ removal remained 65 ± 3%, whereas removal of the competing divalent ions remained near 1%. These results demonstrate that interfacial localization of HMO can preserve its ion-exchange functionality after macroscopic immobilization while enabling selective, regenerable lithium capture under dynamic aqueous conditions.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"5 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2026-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149250942","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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